CN103382026A - Low-cost mass preparation method of high-quality graphene - Google Patents
Low-cost mass preparation method of high-quality graphene Download PDFInfo
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Abstract
The invention discloses a low-cost mass preparation method of high-quality graphene. The low-cost mass preparation method comprises the following steps that graphite and an additive undergo a local or intercalation reaction so that boundary functionalization or intercalated graphite formation is realized; and graphite is peeled by ball milling or an ultrasonic method so that graphene is obtained. The high-quality graphene has water solubility and can forms good graphene hydrosol. Compared with graphene obtained by the traditional chemical peeling method, the high-quality graphene provided by the invention can be prepared simply, has a low cost, less defects, good conductivity and high quality and is suitable for mass production. The high-quality graphene provided by the invention has wide application prospects in photoelectric devices such as copper indium gallium diselenide, cadmium telluride and dye sensitization solar cells and in fields of panel display, supercapacitors, field emitter materials, and lithium ion batteries.
Description
Technical field
The present invention relates to belong to the materials chemistry preparation field, more specifically relate to a kind of low-cost preparation in macroscopic quantity method of high-quality graphene.
Background technology
Graphene is the monoatomic layer material with bi-dimensional cellular shape structure take phenyl ring as elementary cell that is made of carbon atom.Because of the characteristic of its monolayer carbon atom, Graphene is zero gap material, and electron effective mass is zero, and movement velocity is 1/300 light velocity, is the ideal material of physical study; Electronic mobility is up to 200,000cm
2/ V.s, specific conductivity reaches 10
6S/m is conducive to electric charge and effectively collects, and is desirable electrode materials; Visible-to-Near InfaRed transmitance 97.7%, specific surface area are 2600m
2/ g, thermal conductivity can reach 5000W/mK, and intensity can reach 130GPa etc.Therefore, Graphene is expected to obtain in fields such as high-performance nanometer electronic device, matrix material, field emmision material, display device, gas sensor and stored energies widespread use.Due to its unique two-dirnentional structure and excellent crystallography quality, Graphene has contained abundant and novel physical phenomenon, and therefore, Graphene becomes rapidly chemistry, Materials science and Condensed Matter Physics field study hotspot in recent years.
But the prerequisite of Graphene industrial applications is that can magnanimity and low cost, and it will guarantee the quality of Graphene, namely few defective will be arranged.At present, the preparation method of Graphene mainly contains original adoption " micromechanical forces disintegrating method ", namely by mechanical force from graphite crystal sur-face peeling graphene sheet layer and transfer on the carrier surfaces such as silicon oxide.Although this method can prepare the Graphene of micron size, its poor controllability yields poorly; By heating SiC (0001) single-crystal surface extending and growing graphene structure, this Graphene that supports can directly be made electron device by photoetching process, but due to the easily generation reconstruct of surface in high-temperature heating process of SiC plane of crystal, cause surface tissue comparatively complicated, be difficult to obtain the Graphene of big area, thickness homogeneous; Chemical Vapor deposition process (CVD) is take metal single crystal or Polycrystalline Metals film as substrate, expose in its surface and the pyrolytic decomposition carbon compound can generate graphene-structured, but the metal substrate difficulty of growing graphene is removed.At present to use maximum be the chemical stripping method to the preparation Graphene, namely by strong oxidizer graphite oxidation, form graphene oxide, then with strong reductive agent, graphene oxide is reduced into Graphene again.The strong oxidizer that uses in the process of chemical stripping can destroy the carbon skeleton on Graphene plane, produces defective, causes the graphene conductive degradation of gained.Therefore, how the high-quality Graphene of preparation of simple controlled magnanimity is large difficult point and a focus of research at present.
Summary of the invention
The object of the present invention is to provide a kind of method that can the preparation in macroscopic quantity high-quality graphene.In the present invention, utilize organic molecule or salt and graphite to interact in mechanical milling process, make graphite border functionalization.These functional groups can open the graphite border, then are peeled off by ball action, obtain Graphene.
Accordingly, the invention provides a kind of preparation in macroscopic quantity method of high-quality graphene, described method comprises:
(1) make graphite and additive generation local reaction, with graphite border functionalization,
(2) be used for peeling off graphite by extraneous masterpiece, obtain Graphene.
In addition, the present invention also provides a kind of preparation in macroscopic quantity method of high-quality graphene, and described method comprises:
(1) make graphite and additive generation intercalation, form intercalated graphite,
(2) peeled off by extraneous power effect and obtain Graphene.
In embodiments of the present invention, extraneous power used comprises powder crushing technology or ultrasonic lift-off technology.Graphite used is crystalline flake graphite or Graphite Powder 99, and preferably the particle size range of this graphite is the 0.1-200 micron.
In the embodiment of the present invention with graphite border functionalization, additive used is carboxylic acid or the compound that contains carbonyl, is preferably selected from one or more the combination in acetic acid, propionic acid, phenylformic acid, oxalic acid, ethyl acetate, methyl acetate.In the preferred embodiment of the present invention, additive used comprises dry ice.In the preferred embodiment of the present invention, additive used comprises in liquefied ammonia, quadrol, ethanamide, propionic acid amide the combination of one or more.In the preferred embodiment of the present invention, additive used is selected from the salt that contains carbonate, is preferably selected from one or more the mixing in the carbonate such as cobaltous carbonate, nickelous carbonate, iron carbonate, sodium carbonate, sodium bicarbonate, saleratus, volatile salt, bicarbonate of ammonia.
Make in the embodiment of graphite and additive generation intercalation in the present invention, additive used is selected from halogen or halogenide, is preferably selected from one or more the mixing in iodine, bromine, iodine chloride, iodine bromide IBr, iron(ic) chloride, aluminum chloride, cupric chloride, antimony pentachloride.
In the present invention, the mass ratio of described additive and graphite is 0.2-10.
In the present invention, powder crushing technology used is ceramic disintegrating process, preferably planetary ball mill technique, high-energy-milling, sand milling technique, cutting mill technique or gas flow crushing process.Described planetary ball mill technique or high-energy-milling time are 1-100 hour.In described ball-milling technology, the ball grinder internal diameter is 5-50 centimetre, and abrading-ball is of a size of the 2-10 millimeter.The size of described ball grinder and abrading-ball is according to adding the amount of graphite to determine.
In ultrasonic lift-off technology, ultrasonic power used is 50-800 watt, and ultrasonic time is 15-60 minute.
The present invention also provides a kind of Graphene, and this Graphene makes by preparation method of the present invention, and described Graphene has water-soluble.
On the other hand, the invention provides a kind of Graphene water-sol, this Graphene water-sol comprises 0.01-10g/L according to the Graphene of preparation method's gained of the present invention.
On the other hand, a kind of method for preparing graphene film of the present invention, described method comprises:
1) right to use requires 16 described Graphenes, and configuration concentration is the Graphene water-sol of 0.05-0.5g/L;
2) the blend fiber filter membrane as 200nm is filtration medium take the aperture, adds the step 1 of 0.5-1L) in the Graphene water-sol, filtered 6-12 hour, obtain being attached to the graphene film on the blend fiber filter membrane;
3) with step 2) film that obtains under 50-70 ℃ dry 1-3 hour, obtain flexible graphene film;
4) with step 3) the gained graphene film suppresses by the pressure that oil press adds 10-15MPa, obtains fine and close graphene film;
5) with step 4) graphene film under 700-1000 ℃ and inert atmosphere thermal treatment 1-2 hour, make thus graphene film.
Another aspect the invention provides a kind of graphene film, and this graphene film makes by method of the present invention, and described graphene film electric conductivity is 450-1350S/cm.
Compare with the standby Graphene method of traditional chemical stripping legal system, the Graphene defective that the present invention obtains is few, good conductivity, and simple to operate, step is few, preparation cost is very low, can preparation in macroscopic quantity.
The present invention has abandoned traditional " oxidation-peeling off-reduction " preparation Graphene route, develops a kind of efficient stripping means to innovation, has obtained breakthrough on Graphene mass-producing technology of preparing.In addition, the method has avoided using strong Oxidizing and Reducing Agents, has not only avoided the destruction to graphene-structured, has kept high conductivity, and preparation technology simplifies greatly, is easy to amplify produce, and is fit to industrial development.With respect to present commercially available grapheme material and carbon nano-tube material, production cost of the present invention is lower.
Description of drawings
Fig. 1 is the photo in kind of the Graphene water-sol that obtains of the present invention.
Fig. 2 is the mechanism figure that the present invention prepares Graphene.
Primary process is as follows: graphite in mechanical milling process with contain carbonyl or amino Compound Phase mutual effect, make the border of graphite connect carbonyl or the functional group such as amino.Interaction between these functional groups can be opened the border of graphite linings.Under the ball action of ball milling agent, graphite is peeled away along the edge that these open, and obtains Graphene.
Fig. 3 is the transmission electron microscope photo.This photo can be seen the number of plies and the crystallinity of gained Graphene clearly.
Wherein, the sample that obtains as can be known from figure (a) is sheet structure; Fig. 3 (b-c) is the high-resolution electron microscopy photo, therefrom can find out the Graphene number of plies n that obtains＜5; Figure (d) is the electron diffraction pattern figure corresponding with (a), and the electron diffraction pattern of the Graphene of gained of the present invention is the hexagonal symmetry spot, and this explanation has good crystallinity.
Fig. 4 is Raman spectrogram, and it is to characterize Graphene quality and thickness.
Wherein, the Raman spectrogram of the Graphene that (a) obtains for the present invention, the position～2700cm-1 at 2D peak and have good symmetry as can be seen from Figure, the strength ratio I2D/IG=1 at 2D peak and G peak, the peak width at half height at 2D peak is 45cm-1, and the Graphene of this explanation gained of the present invention is layer 2-3; The G peak obviously is better than the D peak, and intensity ratio IG/ID～2.5 illustrate that the Graphene defective that is obtained by the present invention is few.(b) be the Raman spectrogram of graphite raw material, its 2D peak position is at 2725cm-1, and very large acromion is arranged.(c) Raman spectrogram of the Graphene that obtains of chemical stripping method, the ratio IG/ID of G peak and D peak intensity～1.1.
Fig. 5 is photoelectron spectrum.
Wherein, Fig. 5 (a) is full spectrogram, illustrates that the Graphene of gained of the present invention except carbon, only has a small amount of oxygen.Fig. 5 (b) is the narrow scan spectrum of carbon 1s track, and as we know from the figure, it is in conjunction with being 284.5eV, and this is consistent with the combination energy of carbon sp2 atom in Graphene.And the spectrogram of gained has good symmetry, can prove further that thus gained Graphene of the present invention has good quality.
Embodiment
In the present invention, with crystalline flake graphite or Graphite Powder 99 as raw material, in the situation that planetary ball mill or high-energy ball milling, described additive adds as ball milling agent, described ball mill is selected from one or more the mixing in acetic acid, oxalic acid (oxalic acid), ethyl acetate, methyl acetate, the perhaps combination of one or more in liquefied ammonia, quadrol, ethanamide, propionic acid amide, the perhaps mixing of one or more in cobaltous carbonate, nickelous carbonate, sodium bicarbonate, saleratus, bicarbonate of ammonia.The below describes the present invention in detail.
A. Graphene is synthetic
Get graphite and ball milling agent is put into ball grinder, graphite accounts for total material 10%-85%.Add steel ball or copper ball, its volume accounts for ball grinder 1/4-1/2.With planetary ball mill or after high-energy ball milling 6-48 hour, add the water of 0.5-2L, fully stirred 0.5-2 hour, ball milling agent fully is dissolved in water.Filter, washing namely gets graphene powder after drying.The content of ball-milling medium and Ball-milling Time change according to the amount of graphite and the kind of ball-milling medium.
The dried sample of weighing, calculating its productive rate is that every gram graphite can get Graphene 0.7-0.9 gram.
B. the pattern of Graphene and structural characterization
Gained Graphene sample of the present invention is observed the pattern of sample by transmission electron microscope (JEM 2010).Characterize the structure of Graphene with Raman spectrum (Renishaw invia Raman Microscope, excitation wavelength is 514.5nm).
Each element relative content ratio and chemical combination attitude thereof with x-ray photoelectron spectroscopy (XPS) analytic sample surface.Instrument is the PHI 5000C ESCA System of U.S. PHI company; The employing condition is the magnesium target, high pressure 14.0kV, and power 250W, vacuum is better than 1 * 10
-8Torr.The RBD147 data collecting card of employing U.S. RBD company and AugerScan3.21 software is the full scan spectrum (lead to and can be 93.9eV) of 0～1200eV of collected specimens respectively, then gather the narrow scan spectrum (lead to and to be 23.5eV) of each element related track, and adopt AugerScan3.21 software to carry out data analysis.Characterize by XPS, the Graphene composition of gained of the present invention only contains a small amount of oxygen except carbon, and the oxygen level scope is 3.5-8.6atom%.Wherein partial oxygen is also from the oxygen of sample absorption.
Measure the electroconductibility of Graphene with four point probe Van Der Pauw method (Accent HL5500).
Its electroconductibility that compares with Graphene of the present invention and chemical stripping method (being the Hummers method) preparation.
C. the chemical stripping legal system is for Graphene (as a comparative example)
Prepare the electroconductibility of Graphene for contrast the present invention, with the standby graphene oxide that obtains of Hummers legal system, namely obtain graphite oxide with the vitriol oil, SODIUMNITRATE and potassium permanganate oxidation flake graphite, obtain graphene oxide [W.S.Hummers, etc.J.Am.Chem.Soc. (1958) 1339] with ultrasonic peeling off again.Rear method with high temperature pyrolysis is come redox graphene (r-GO).
D. the preparation of graphene film
Electroconductibility is the important indicator of proof Graphene quality, and good electroconductibility is the prerequisite that Graphene further utilizes.For this reason, Graphene is prepared into film as follows.
(1) the gained Graphene is dispersed in water, it is the Graphene water-sol of 0.05-0.5g/L that configuration forms concentration, as shown in Figure 1.Graphene concentration is determined according to film thickness.
(2) be prepared into graphene film with vacuum filtration process.Blend fiber filter membrane take the aperture as 200nm is filtration medium, adds the Graphene water-sol of 0.5-1L.Filtered 6-12 hour, and obtained being attached to the graphene film on the blend fiber filter membrane.
(3) with the film that obtains under 50-70 ℃ dry 1-3 hour, namely get flexible graphene film.
(4) in order to increase the contact of graphene film interlayer, the gained graphene film with oil press, is added the pressure press membrane of 10-15MPa, obtain finer and close graphene film.
(5) in order further to increase the interaction between Graphene, with the graphene film of gained under 800 ℃, with inert atmosphere protection thermal treatment 1-2 hour.
(6) measure the electroconductibility of graphene film with four point probe Van Der Pauw method (Accent HL5500).The electric conductivity that records gained Graphene of the present invention is 450-1350S/cm.Best electric conductivity is better than the bibliographical information optimum value.
The below introduces embodiments of the invention, and to understanding of the present invention, but the present invention is limited to absolutely not embodiment with further increase.
Synthesizing of Graphene of the present invention
Get 5 gram 100 purpose crystalline flake graphites (particle diameter is less than 150 μ m) and put into the oxalic acid of 15 grams the ball grinder that internal diameter is 10cm, adding the particle diameter that accounts for ball grinder volume 1/3 is the stainless steel bead of 5mm.After tightening ball grinder, put into high energy ball mill.Be under 500rpm at rotating speed, ball milling added the deionized water of 1L after 24 hours, and Graphene is washed out.Fully stirred 1 hour, guarantee that oxalic acid all is dissolved in water.Filter, and with the deionized water wash of 1L, obtain graphene powder after vacuum-drying.
Weighing obtains the Graphene of 4.45g.Calculating its productive rate is that every gram graphite can get Graphene 0.89 gram.
The standby Graphene of chemical stripping legal system in prior art
The electroconductibility of the excellence of the Graphene for preparing for outstanding the present invention, we are with chemical stripping legal systems standby Graphene, i.e. Hummers method.
Get the flake graphite of 1.0g, the SODIUMNITRATE (NaNO of 1g
3) and the vitriol oil of 46ml stirred in ice bath 15 minutes, add slowly the potassium permanganate (KMnO of 6g
4).After mixing, system is transferred in the water-bath of 35 ± 5 ℃, stirred 6 hours, form the mixture of the mud sample of black.
Under agitation condition, add the deionized water of 20ml in the mixture, system temperature is raised to 90 ± 5 ℃.The water dilution that adds 200ml after 30min.The H that adds 6ml
2O
2(30%) the excessive KMnO of reduction
4, the system color is glassy yellow by brown stain.
With solution filter obtained above, and wash with a large amount of water (being about 2L).The filter cake that obtains is dispersed in deionized water again, ultra-sonic dispersion 20min.With the whizzer centrifugal 5min under low speed 1000rpm of elder generation, to remove the graphite that does not react completely, rear water in high speed 12000rpm removes graphene oxide.Namely get graphene oxide after 100 ℃ of dry 8h of vacuum again.
With the graphene oxide that obtains at H
2/ Ar (contains 5% H
2) be heated to 1000 ℃ in gas mixture, insulation 6h, reduction obtains Graphene.
The preparation of graphene film and the test of electroconductibility
(1) get ultrasonic 15 minutes of the Graphene of 0.1g gained gained of the present invention, be dispersed in 1L water, it is the Graphene water-sol of 0.1g/L that configuration forms concentration.
(2) the blend fiber filter membrane as 200nm is filtering membrane take the aperture, adds the above-mentioned Graphene water-sol of 1L.Filtered 12 hours, and obtained being attached to the graphene film on the blend fiber filter membrane.
(3) with the film that obtains under 60 ℃ dry 1 hour, namely get flexible graphene film.
(4) in order to increase the contact of graphene film interlayer, the gained graphene film with oil press, is added the pressure press membrane of 10MPa, obtain finer and close graphene film.
(5) can transfer to any substrate with the graphene film after acetone solution blend fiber filter membrane.
(6) in order further to increase the interaction between Graphene, the graphene film of gained is transferred on quartz substrate, under 800 ℃, with inert atmosphere protection thermal treatment 2 hours.
(7) measure the electroconductibility of graphene film with four point probe Van Der Pauw method.The electric conductivity that records gained Graphene of the present invention is 1150S/cm.Best electric conductivity is better than the bibliographical information optimum value.
Redox Graphene (r-GO) thin film technology method and aforesaid method are similar, and difference is, r-GO is replaced the Graphene of gained of the present invention.Finally recording its electric conductivity is 84S/cm.
This explanation is compared with the Graphene that traditional oxidation reduction process prepares, and the Graphene defective of gained of the present invention is few, quality is high.And preparation process of the present invention is very simple, and cost is very low, does not relate to again toxic substance, and therefore, the present invention has very significantly advantage in suitability for industrialized production.
Embodiment 2
Get 5 gram 100 purpose crystalline flake graphites (particle diameter is less than 150 μ m) and put into the dry ice of 500 grams the ball grinder that internal diameter is 10cm, adding the particle diameter that accounts for ball grinder volume 1/3 is the stainless steel bead of 5mm.After tightening ball grinder, put into high energy ball mill.Be under 500rpm at rotating speed, ball milling was opened ball grinder after 48 hours, namely got graphene powder after allowing dry ice fully volatilize.Weighing obtains the Graphene of 4.01g.Calculating its productive rate is that every gram graphite can get Graphene 0.8 gram.
The present invention's ball milling agent used is the dry ice of nontoxic cheapness, has saved washing and filtering and dry process.Make process of the present invention simpler.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 1085S/cm.
Embodiment 3
Get the liquefied ammonia of 5 gram 100 purpose crystalline flake graphites (particle diameter is less than 150 μ m) and 3mL, put into the stainless steel jar mill that internal diameter is 10cm, adding the particle diameter that accounts for ball grinder volume 1/3 is the stainless steel bead of 5mm.After tightening ball grinder, put into high energy ball mill.Be under 600rpm at rotating speed, ball milling was opened ball grinder after 20 hours in ventilating kitchen, namely got graphene powder after allowing ammonia fully volatilize.Weighing obtains the Graphene of 4.25g.Calculating its productive rate is that every gram graphite can get Graphene 0.85 gram.
The present invention's ball milling agent used is liquefied ammonia, has saved washing and filtering and dry process.Make process of the present invention simpler.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 945S/cm.
Embodiment 4
Get the cobaltous carbonate of 10 gram 100 purpose crystalline flake graphites (particle diameter is less than 150 μ m) and 50 grams, put into the stainless steel jar mill that internal diameter is 10cm, adding the particle diameter that accounts for ball grinder volume 1/2 is the stainless steel bead of 5mm.After tightening ball grinder, put into high energy ball mill.Be under 700rpm at rotating speed, ball milling was opened ball grinder after 48 hours, added the deionized water of 500mL that mixture is washed out.Under whipped state, add the concentrated hydrochloric acid of 200mL, fully stirred 2 hours, to remove the ball-milling medium cobaltous carbonate fully.Filter, and with the deionized water wash of 1L, obtain graphene powder after lyophilize.Weighing obtains the graphene powder of 8.5g.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 525S/cm.
Get the sodium bicarbonate of 10 gram 100 purpose crystalline flake graphites (particle diameter is less than 150 μ m) and 40 grams, put into the stainless steel jar mill that internal diameter is 10cm, adding the particle diameter that accounts for ball grinder volume 1/2 is the stainless steel bead of 5mm.After tightening ball grinder, put into high energy ball mill.Be under 700rpm at rotating speed, ball milling was opened ball grinder after 48 hours, added the deionized water of 500mL that mixture is washed out.Under whipped state, add the concentrated hydrochloric acid of 50mL, fully stirred 2 hours, to remove the ball-milling medium sodium bicarbonate fully.Filter, and with the deionized water wash of 1L, obtain graphene powder after lyophilize.Weighing obtains the graphene powder of 8.6g.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 650S/cm.
Embodiment 6
Get the 5g particle diameter and be the ethyl acetate of 100 purpose crystalline flake graphites (less than 150 μ m) and 20mL, then the sodium-chlor that adds 15g is as ball-milling medium.Adding the particle diameter that accounts for ball grinder volume 1/4 is the stainless steel bead of 5mm.After tightening ball grinder, put into high energy ball mill.Be under 500rpm at rotating speed, ball milling added the deionized water of 1L after 12 hours, and Graphene is washed out.Fully stirred 1 hour, guarantee that sodium-chlor and ethyl acetate all are dissolved in water.Filter, and with the deionized water wash of 1L, obtain graphene powder after lyophilize.Weighing obtains the Graphene of 4.5g.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 480S/cm.
Embodiment 7
Get the nickelous carbonate of 10 gram 100 purpose crystalline flake graphites (particle diameter is less than 150 μ m) and 40 grams, put into the stainless steel jar mill that internal diameter is 10cm, adding the particle diameter that accounts for ball grinder volume 1/2 is the stainless steel bead of 5mm.After tightening ball grinder, put into high energy ball mill.Be under 600rpm at rotating speed, ball milling was opened ball grinder after 48 hours, added the deionized water of 500mL that mixture is washed out.Under whipped state, add the concentrated hydrochloric acid of 50mL, fully stirred 2 hours, to remove the ball-milling medium cobaltous carbonate fully.Filter, and with the deionized water wash of 1L, obtain graphene powder after lyophilize.Weighing obtains the graphene powder of 7.45g.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 450S/cm.
Embodiment 8
Get the bicarbonate of ammonia of 10 gram 100 purpose crystalline flake graphites (particle diameter is less than 150 μ m) and 50 grams, put into the stainless steel jar mill that internal diameter is 10cm, adding the particle diameter that accounts for ball grinder volume 1/2 is the stainless steel bead of 5mm.After tightening ball grinder, put into high energy ball mill.Be under 600rpm at rotating speed, ball milling was opened ball grinder after 48 hours, added the deionized water of 500mL that mixture is washed out.Under whipped state, add the concentrated hydrochloric acid of 50mL, fully stirred 2 hours, to remove the ball-milling medium cobaltous carbonate fully.Filter, and with the deionized water wash of 1L, obtain graphene powder after lyophilize.Weighing obtains the graphene powder of 8.92g.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 760S/cm.
Embodiment 9
Get the dry ice of 5 gram 100 purpose crystalline flake graphites (particle diameter is less than 150 μ m) and 30 grams and put into the ball grinder that internal diameter is 10cm, then the sodium-chlor that adds 15 grams is as ball-milling medium.Adding the particle diameter that accounts for ball grinder volume 1/4 is the stainless steel bead of 5mm.After tightening ball grinder, put into high energy ball mill.Be under 500rpm at rotating speed, ball milling was opened ball grinder after 12 hours, namely got graphene powder after allowing dry ice fully volatilize.Weighing obtains the Graphene of 4.01g.Calculating its productive rate is that every gram graphite can get Graphene 0.87 gram.
Compare with embodiment 2, add sodium-chlor as ball-milling medium in the present embodiment 9, can obviously improve grinding efficiency, reduce Ball-milling Time.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 1350S/cm.
Embodiment 10
Get 5 gram 100 purpose crystalline flake graphites (particle diameter is less than 150 μ m), the liquefied ammonia of 2mL and the bicarbonate of ammonia of 10g, put into the stainless steel jar mill that internal diameter is 10cm, adding the particle diameter that accounts for ball grinder volume 1/3 is the stainless steel bead of 5mm.After tightening ball grinder, put into high energy ball mill.Be under 600rpm at rotating speed, ball milling was opened ball grinder after 12 hours in ventilating kitchen, and after allowing ammonia fully volatilize, water washes out the mixture of Graphene and bicarbonate of ammonia.The strong brine that under agitation adds 50mL is with abundant dissolving bicarbonate of ammonia.Namely get graphene powder after filtration, washing, lyophilize.Weighing obtains the Graphene of 4.25g.
Compare with embodiment 3, add sodium-chlor as ball-milling medium in the present embodiment 10, can obviously improve grinding efficiency, reduce Ball-milling Time.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 1145S/cm.
Embodiment 11
Get the liquefied ammonia of 5 gram particle footpath 200 μ m and 10mL, put into round-bottomed flask.Flask is placed in the mixture of dry ice and acetone, non-volatile with the liquefied ammonia of going bail for.Fully stir after three hours, transfer in ultrasonic apparatus.Under 250 watts ultrasonic 30 minutes.After fully volatilizing, ammonia namely obtains graphene powder.Weighing obtains the Graphene of 4.64g.
The present invention's ball milling agent used is liquefied ammonia, has saved washing and filtering and dry process.Make process of the present invention simpler.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 785S/cm.
Embodiment 12
Get the iodine chloride of 5 gram 100 purpose crystalline flake graphites (particle diameter is less than 150 μ m) and 1mL, put into internal diameter and be the alumina balls grinding jar of 5 centimetres.Adding particle diameter is the alumina globule of 3 millimeters.After sealing, planetary ball mill is 12 hours.After opening ball grinder, add the water of 200mL, wash out mixture.Obtain graphene powder after stirring, filtration, washing, drying.Weighing obtains the Graphene of 4.03g.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 1078S/cm.
Embodiment 13
Get the Graphite Powder 99 of 2 gram particle footpath 0.1 μ m and the iodine chloride of 5mL, put into the round-bottomed flask of 50mL.Be placed in the oil bath of 120 ℃, insulation 6h.After taking-up, be placed in ultrasonic 20 minutes of the ultrasonic apparatus of 150 watts.Add 500mL to wash out mixture.By obtaining 4.68 gram graphene powders after stirring, filtration, washing, drying.
The preparation of graphene film and the test of electroconductibility thereof such as embodiment 1, recording electric conductivity is 1298S/cm.
Claims (19)
1. the preparation in macroscopic quantity method of a high-quality graphene, described method comprises:
(1) make graphite and additive generation local reaction, with graphite border functionalization,
(2) be used for peeling off graphite by extraneous masterpiece, obtain Graphene;
Wherein, described additive is selected from carboxylic acid, contains compound, dry ice, liquefied ammonia, the compound of amino-contained, the salt that contains carbonate or their combination of carbonyl.
2. the preparation in macroscopic quantity method of a high-quality graphene, described method comprises:
(1) make graphite and halogen or halogenide generation intercalation, form intercalated graphite,
(2) peeled off by extraneous power effect and obtain Graphene.
3. by the described preparation in macroscopic quantity method of claim 1-2 any one, it is characterized in that, described extraneous power comprises powder crushing technology or ultrasonic lift-off technology.
4. by the described preparation in macroscopic quantity method of claim 1-2 any one, it is characterized in that, described graphite is crystalline flake graphite or Graphite Powder 99, and preferably the particle size range of this graphite is the 0.1-200 micron.
5. by preparation in macroscopic quantity method claimed in claim 1, it is characterized in that, described carboxylic acid is selected from one or more the combination in acetic acid, propionic acid, phenylformic acid, oxalic acid.
6. by preparation in macroscopic quantity method claimed in claim 1, it is characterized in that, the described compound that contains carbonyl is selected from one or more the combination in ethyl acetate, methyl acetate.
7. by preparation in macroscopic quantity method claimed in claim 1, it is characterized in that, the compound of described amino-contained is selected from quadrol, ethanamide, propionic acid amide the combination of one or more.
8. by preparation in macroscopic quantity method claimed in claim 1, it is characterized in that, the described salt that contains carbonate is selected from one or more the mixing in the carbonate such as cobaltous carbonate, nickelous carbonate, iron carbonate, sodium carbonate, sodium bicarbonate, saleratus, volatile salt, bicarbonate of ammonia.
9. by preparation in macroscopic quantity method claimed in claim 2, it is characterized in that, described halogen or halogenide are selected from one or more the mixing in iodine, bromine, iodine chloride, iodine bromide IBr, iron(ic) chloride, aluminum chloride, cupric chloride, antimony pentachloride.
10. by the described preparation in macroscopic quantity method of claim 5-9 any one, it is characterized in that, the mass ratio of described additive and graphite is 0.2-10.
11. by preparation in macroscopic quantity method claimed in claim 3, it is characterized in that, described powder crushing technology is ceramic disintegrating process, preferably planetary ball mill technique, high-energy-milling, sand milling technique, cutting mill technique or gas flow crushing process.
12. by the described preparation in macroscopic quantity method of claim 11, it is characterized in that, described planetary ball mill technique or high-energy-milling time are 1-100 hour.
13. by the described preparation in macroscopic quantity method of claim 12, it is characterized in that, in described ball-milling technology, the ball grinder internal diameter is 5-50 centimetre, abrading-ball is of a size of the 2-10 millimeter.
14. by the described preparation in macroscopic quantity method of claim 13, it is characterized in that, the size of described ball grinder and abrading-ball is according to adding the amount of graphite to determine.
15. by preparation in macroscopic quantity method claimed in claim 3, it is characterized in that, in ultrasonic lift-off technology, described ultrasonic power is 50-800 watt, ultrasonic time is 15-60 minute.
16. a Graphene, this Graphene makes by the described preparation method of claim 1-15 any one, and described Graphene has water-soluble.
17. a Graphene water-sol, this Graphene water-sol comprise 0.01-10g/L according to the Graphene of the described preparation method's gained of claim 1-15 any one.
18. a method for preparing graphene film, described method comprises:
1) right to use requires 16 described Graphenes, and configuration concentration is the Graphene water-sol of 0.05-0.5g/L;
2) the blend fiber filter membrane as 200nm is filtration medium take the aperture, adds the step 1 of 0.5-1L) in the Graphene water-sol, filtered 6-12 hour, obtain being attached to the graphene film on the blend fiber filter membrane;
3) with step 2) film that obtains under 50-70 ℃ dry 1-3 hour, obtain flexible graphene film;
4) with step 3) the gained graphene film suppresses by the pressure that oil press adds 10-15MPa, obtains fine and close graphene film;
5) with step 4) graphene film under 700-1000 ℃ and inert atmosphere thermal treatment 1-2 hour, make thus graphene film.
19. a graphene film, this graphene film makes by the described method of claim 18, and described graphene film electric conductivity is 450-1350S/cm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704520A (en) * | 2009-11-05 | 2010-05-12 | 华侨大学 | Method for producing graphene |
| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
-
2012
- 2012-05-02 CN CN2012101345772A patent/CN103382026A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704520A (en) * | 2009-11-05 | 2010-05-12 | 华侨大学 | Method for producing graphene |
| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
Non-Patent Citations (5)
| Title |
|---|
| CHIH-JEN SHIH, ET AL.: "Bi- and trilayer graphene solutions", 《NATURE NANOTECHNOLOGY》 * |
| WEIFENG ZHAO, ET AL.: "Preparation of graphene by exfoliation of graphite using wet ball milling", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| XUAN WANG, ET.AL.: "Transparent, Conductive Graphene Electrodes for Dye-Sensitized Solar Cells", 《NANO LETTERS》 * |
| 杨勇辉等: "石墨烯薄膜的制备和结构表征", 《物理化学学报》 * |
| 江莞等: "机械剥离法制备石墨烯及其在石墨烯/陶瓷复合材料制备中的应用", 《中国材料进展》 * |
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